Composition of matter for oxidative conversion of organic compounds

ABSTRACT

A solid composition of matter consisting essentially of: 
     (a) a component comprising: (1) at least one metal selected from the group consisting of Group IA metals and compounds containing said metals and (2), optionally, at least one material selected from the group consisting of tin, compounds containing tin, chloride ions and compounds containing said chloride ions and 
     (b) a component comprising at least one metal selected from the group consisting of Group IIA metals and compounds containing said metals. 
     The composition is particularly useful as a contact material for the oxidative conversion of less valuable organic compounds to more valuable organic compounds, particularly in the presence of a free oxygen containing gas. A method for converting feed organic compounds to product organic compounds, in the presence of a free oxygen containing gas, utilizing the above composition, as well as combinations of tin and a Group IIA metal and of tin, chloride ions and a Group IIA metal is disclosed, particularly the oxidative dehydrogenation of C 2  to C 7  alkanes to olefins.

This application is a Division of application Ser. No. 713,674, filedMar. 19, 1985, now U.S. Pat. No. 4,672,145.

The present invention relates to an improved composition of matter. In amore specific aspect, the present invention relates to an improved solidcontact material for the oxidative conversion of feed organic compoundsto product organic compounds. In yet another aspect, the presentinvention relates to a solid contact material for the oxidativeconversion of feed organic compounds to product organic compounds, inthe presence of a free oxygen containing gas and a method for suchconversion.

BACKGROUND OF THE INVENTION

Numerous processes are in use and have been proposed for the conversionof organic compounds and feedstocks to more valuable organic compoundsand more valuable feedstocks for use in the organic chemical andpetrochemical industries, particularly organic compounds and feedstocksderived from petroleum sources.

One promising approach to such conversion has been the oxidativeconversion of organic compounds to other organic compounds. However, inmany cases, such oxidative conversion processes are not commerciallyviable, primarily because they are energy intensive, conversions of thefeedstock are low, selectivity to the desired compounds is low and suchprocesses cannot be utilized in a continuous manner. In most of suchprocesses the feedstocks are contacted with a solid contact material.However, there is a difference of opinion among workers in the artconcerning the nature of such processes, and, particularly, the functionof the contact material and the manner in which such function isperformed. For example, workers in the art have at one time or anothersuggested that the function of the contact material involves a purelyphysical phenomenon, an adsorption-desorption process, either of atomicor molecular oxygen, either on the surface or occluded within the solidmaterial, oxidation-reduction, utilizing multivalent metals capable ofoxidation-reduction, adsorption and desorption of the organic materialson the solid materials, a free radical mechanism, etc. Consequently, thesolid materials utilized are referred to variously as "contactmaterials", "promoters", "activators" and "catalysts". Accordingly, inorder to avoid functional categorization, the terms "solid contactmaterial" or "solid contact materials" will be utilized in the presentapplication.

Since many processes of the prior art are based on the theory that thecontact materials function via adsorption-desorption of oxygen,oxidation-reduction, etc., such processes are operated in a cyclicmanner by passing an oxidizing gas over the contact material, thencontacting the feedstock with the oxygen-containing contact material,and, thereafter, reactivating or regenerating the contact material byagain passing an oxidizing gas thereover. Such processes thus requireundesirably high temperatures, are energy intensive, since theexothermic and endothermic reactions occur separately, equipment costsare high, because of the necessity for rapid cycling, and the contactmaterial's useful life is comparatively short.

From the above, it is quite clear that the suitability of contactmaterials for the oxidative conversion of organic compounds isunpredictable. It is, therefore, highly desirable that new and improvedcontact materials for such use be developed, and that improved processesutilizing such contact materials be provided, particularly processeswhich lower the temperatures necessary, lower the energy requirements,are capable of being carried out in a continuous manner, extend theuseful life of the contact material, improve the conversion of thefeedstock and improve the selectivity to the desired products.

Of the various feedstocks for the organic chemical and petrochemicalindustries, olefins, such as ethylene and propylene are of particularinterest and have become major feedstocks. Of these, ethylene is by farthe more important chemical feedstock since the demand for ethylenefeedstocks is about double that for propylene feedstocks. Consequently,there is a definite need for materials and processes for the conversionof relatively inexpensive feedstocks to ethylene. At the present time,ethylene is produced almost exclusively by the dehydrogenation orpyrolysis of ethane and propane, naptha and, in some instances, gasoils. About 75% of the ethylene is produced at the present time by steamcracking of ethane and propane derived from natural gas, since naturalgas contains from about 5 volume percent to about 60 volume percent ofhydrocarbons other than methane, with the majority being ethane.However, relatively severe conditions, particularly temperatures inexcess of about 1000° C., are required and, as indicated, such processesare highly energy intensive. In order to reduce the severity of theconditions, particularly temperature, numerous proposals to catalyzepyrolytic reactions have been made. While some of these processes do, infact, reduce the severity of the conditions, the conversion of thefeedstock and the selectivity to ethylene are still quite low. Ofparticular interest in this phase of the art, is the oxidativedehydrogenation of alkanes, particularly alkanes having from 2 to 7carbon atoms, and, still more particularly, ethane. However, many of theprocesses for oxidative dehydrogenation, which have been proposed, aresubject to some or all of the previously mentioned deficiencies.

SUMMARY OF THE INVENTION

It is therefore an object of the present invention to provide animproved composition of matter and method of utilizing the same whichovercomes the above and other disadvantages of the prior art. Anotherobject of the present invention is to provide an improved composition ofmatter. Yet another object of the present invention is to provide animproved contact material for the oxidative conversion of organiccompounds to other organic compounds. Still another object of thepresent invention is to provide an improved contact material for theoxidative conversion of organic compounds to other organic compounds, inthe presence of a free oxygen containing gas. Another and further objectof the present invention is to provide an improved method for theoxidative conversion of organic compounds to other organic compounds inthe presence of a free oxygen containing gas. Another and further objectof the present invention is to provide an improved method for theoxidative conversion of alkane hydrocarbons to other hydrocarbons in thepresence of a free oxygen containing gas. A further object of thepresent invention is to provide a method for the oxidative conversion oforganic compounds to other organic compounds having an improvedconversion of feedstock. Yet another object of the present invention isto provide a method for the oxidative conversion of organic compounds toother organic compounds having an improved selectivity to desiredproducts. A further object of the present invention is to provide amethod for the oxidative conversion of organic compounds to otherorganic compounds having an improved conversion of feedstock and animproved selectivity to desired products. Another and further object ofthe present invention is to provide a method for the oxidativeconversion of organic compounds to other organic compounds whichutilizes temperatures below those of known processes. A still furtherobject of the present invention is to provide a method for the oxidativeconversion of organic compounds to other organic compounds which reducesthe energy requirements thereof. Another object of the present inventionis to provide a method for the oxidative conversion of organic compoundsto other organic compounds which can be carried out in a continuousmanner. Yet another object of the present invention is to provide amethod for the oxidative conversion of organic compounds to otherorganic compounds which extends the useful life of the contact materialutilized. These and other objects of the present invention will beapparent from the following detailed description.

The present invention provides an improved, solid composition of matterconsisting essentially of:

(a) a component comprising (1) at least one metal selected from thegroup consisting of Group IA metals, and compounds containing saidmetals and (2), optionally, at least one material selected from thegroup consisting of tin, compounds containing tin, chloride ions andcompounds containing said chloride ions and

(b) a component comprising at least one metal selected from the groupconsisting of Group IIA metals and compounds containing said metals.

In still another aspect, the present invention relates to a solidcontact material, of the specified character, for the oxidativeconversion of feed organic compounds to product organic compounds, inthe presence of a free oxygen containing gas. The present inventionfurther provides an improved method for the oxidative conversion of feedorganic compounds to product organic compounds in which the free organiccompounds and a free oxygen containing gas are contacted with a solidcontact material, under conditions sufficient to produce such otherproduct organic compounds, and, still more particularly, an improvedmethod for such oxidative conversion of alkane hydrocarbons to otherhydrocarbons, desirably ethylene.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The improved, solid composition of matter of the present invention is asolid composition of matter consisting essentially of:

(a) a component comprising: (1) at least one metal selected from thegroup consisting of Group IA metals and compounds containing said metalsand (2), optionally, at least one material selected from the groupconsisting of tin, compounds containing tin, chloride ions and compoundscontaining said chloride ions and

(b) a component comprising at least one metal selected from the groupconsisting of a Group IIA metal and compounds containing said metal.

Particularly useful Group IA metals are selected from the groupconsisting of lithium, sodium and potassium, and, still moreparticularly, lithium. Group IIA metals, preferably, are selected fromthe group consisting of magnesium, calcium, strontium and barium and,still more particularly, magnesium and calcium.

These compositions of matter and contact materials are particularlyuseful for the oxidative conversion of organic compounds to otherorganic compounds, and, particularly, the conversion of organiccompounds to other organic compounds, in the presence of a free oxygencontaining gas. Processes of this character include the oxidativedehydrogenation of hydrocarbons, particularly alkanes having 2 to 7carbon atoms, to other hydrocarbons, particularly ethylene, theoxidative conversion of methane to higher hydrocarbons, particularlyethylene, the oxidative methylation of toluene, in the presence ofmethane, to ethyl benzene and styrene, the oxidative conversion oftoluene to stilbene, the oxidative methylation of acetonitrile, in thepresence of methane, to acrylonitrile and C₂ + hydrocarbons and theoxidative methylation of other hydrocarbons. The compositions of matterof the present invention are particularly useful for the oxidativedehydrogenation of alkane hydrocarbons to other hydrocarbons,particularly the oxidative dehydrogenation of alkanes having from 2 to 7carbon atoms to ethylene, in the presence of a free oxygen containinggas.

The above compositions of matter as well as compositions containing tinin combination with Group IIA metals have been found quite effective forthe oxidative conversion of feed organic compounds to product organiccompounds, in the presence of a free oxygen containing gas, particularlythe oxidative conversion of alkanes having 2 to 7 carbon atoms, as anethane-containing gas, to olefins, particularly ethylene. Specifically,in accordance with the present invention, feed organic compounds areconverted to product organic compounds by contacting feed organiccompounds, such as alkanes having 2 to 7 carbon atoms, particularly anethane-containing gas, and a free oxygen containing gas with a solidcomposition of matter consisting essentially of:

(a) a component comprising:

(1) at least one metal selected from the group consisting of Group IAmetals, tin and compounds containing said metals and (2) optionally atleast one material selected from the group consisting of chloride ionsand compounds containing said chloride ions and

(b) a component comprising: at least one metal selected from the groupconsisting of Group IIA metals and compounds containing said metals

under conditions sufficient to convert said feed organic compounds tosaid product organic compounds.

When the term "effective amount" is utilized with reference to thecomposition of matter and contact material herein, this term is meant toinclude more than an insignificant amount and, thus, a small amountsufficient to affect the function of the composition of matter for thepurpose for which it is to be utilized.

Thus, the above compositions of matter contain from an effective amountof the Group IA metal to near 100 wt. %, so long as an effective amountof the Group IIA metal is present, preferrably, a minor amount andusually from 0.1 to 50 wt. % of the Group IA metal (expressed as ametal) and, still more preferably, between about 0.5 and about 15 wt. %and, optimally, between about 1 and about 5 wt. %. Where tin isutilized, it is present in an effective amount to near 100 wt. %,usually in amounts between about 0.5 and 20 wt. %, and, preferably,between about 1 and about 7 wt. %. Chloride, when present, is utilizedin amounts from an effective amount to near 100 wt. %, usually betweenabout 0.1 and about 5 wt. %, expressed as elemental chlorine. The weightpercent designations given are the weight percent of the indicatedelement based on the total weight of the solid composition of matter orcontact material, including the Group IIA metal compound and thecompound or compounds in which the element or elements are present.

The above-mentioned components can be mixed with or deposited on an"inert support material" adapted to harden or support the activematerials. The term "inert support material", when utilized in thiscontext, is meant to include any material which does not react with orexchange ions with the active components, has no significant functionaleffect on the production of desired or undesired products in the processfor which the solid contact material is utilized and functions only as ahardening agent or support for the active components. Where such solidsupport material is utilized the weight of such solid support materialis not included in determining the relative weights of the activecomponents.

The Group IA metal, tin, and Group IIA metal can be derived from anysuitable source of such materials, such as metal carbonates, oxides,nitrates, octoates and chlorides. The chlorine may be an organic orinorganic chloride. The composition of matter can be prepared by anysuitable method known in the art for the preparation of such materialsin solid form. Particularly effective techniques are those utilized forthe preparation of solid catalysts. Conventional methods includecoprecipitation from an aqueous, an organic or a combinationsolution-dispersion, impregnation, dry mixing, wet mixing or the like,alone or in various combinations. In general, any method can be usedwhich provides compositions of matter containing the prescribedcomponents in effective amounts. For example, a lithium/magnesiummaterial may be produced by mixing lithium carbonate and magnesium oxidein a blender with enough water to form a thick slurry. The slurry canthen be dried, usually at a temperature sufficient to volatilize thewater or other carrier, such as about 220° F. to about 450° F.Alternatively, magnesium oxide pellets can be impregnated with anaqueous solution of lithium nitrate and dried. Where tin is present, thecomposition can be produced by impregnating magnesium oxide pellets witha hexane solution of tin octoate and drying. Lithium/tin/magnesiumcompositions can be produced by impregnating magnesium oxide pelletswith a hexane solution of tin octoate and an aqueous solution of lithiumnitrate and drying. In all cases, irrespective of how the components arecombined, and irrespective of the source of the metal or chloride, thedried composition is calcined in the presence of a free oxygencontaining gas, usually at temperatures between about 700° F. and about1200° F. for from 1 to about 24 hours. While the exact form of themetals in the resultant composition is not known, it is believed thatthe Group IA and Group IIA metals are predominantly in their oxide formand, where chlorine is present, it is in the form of a chloride. Whereboth tin and chloride ions are present they can be added in the form oftin chloride.

The oxidative dehydrogenation of alkanes to other hydrocarbons,particularly ethane to ethylene, can be carried out under a wide rangeof conditions. Since conditions which favor high conversion of feedstockgenerally result in lower selectivities to the desired products, andvice versa, the conversion and selectivity can be balanced, as desired,to some extent, by selecting the composition of the contact material,and/or varying the conditions of operation.

In any event, the feed rate of the hydrocarbon feedstock will generallybe between about 100 and about 1000 GHSV, and, preferably, between about400 and about 500 GHSV. When air is, utilized as a source of freeoxygen, a feed rate of about 200 to about 10,000 GHSV and preferablyabout 1200 to 1500 GHSV is utilized. The volumetric ratio of gaseousfeed components, specifically ethane to free oxygen, will be betweenabout 1/1 and about 30/1 and preferably about 1/1 and about 3/1. Inertgases such as nitrogen, helium and the like can be utilized as a diluentor a substitute for the nitrogen of air, when the free oxygen containinggas is oxygen or an oxygen-enriched air. Reaction temperatures may varybetween about 600° C. and about 775° C., and are, preferably, betweenabout 650° C. and 725° C. Total pressures may vary from about 0.5 toabout 10 atmospheres and are preferably around 1 atmosphere.

The nature and the advantages of the present invention are illustratedby the following examples of the oxidative dehydrogenation of ethane, inthe presence of a free oxygen containing gas.

A contact material comprising magnesium oxide alone was prepared bycalcining magnesium oxide pellets at 815° C. in the presence of air.Lithium/magnesium oxide contact materials were prepared by impregnating50 grams of magnesium oxide pellets with 2.1 grams lithium nitratedissolved in 50 milliliters of water. After impregnation, the contactmaterial was dried at 120° C. and then calcined for 3 hours at 815° C.in air. This resulted in the contact material having a calculatedlithium content of 0.5 wt. %. A tin/magnesium oxide contact material wasprepared by impregnating 40 grams of magnesium oxide with 4.35 grams oftin octoate dissolved in 60 milliliters of hexane. The composition wasthen dried and calcined at 815° C. for 3 hours in air. This resulted ina material having 2.5 wt. % of tin. A lithium/tin/magnesium oxidecontact material was prepared by impregnating 40 grams of magnesiumoxide with 4.35 grams of tin octoate dissolved in 60 milliliters ofhexane, drying the same and, thereafter, impregnating with 2.1 grams oflithium nitrate dissolved in 60 milliliters of water. The contactmaterial was again dried and calcined for 3 hours at 815° C. in air.This contact material contained 6.3 wt. % lithium and 2.5 wt. % tin. Acontact material of tin/chloride/magnesium oxide was prepared byimpregnating 40 grams of magnesium oxide with 10.7 grams of tin chloride(SnCl₄) dissolved in 50 ml of water. The resultant material was dried at100° C. and then calcined at 815° C. This contact material wascalculated to contain 8.2 wt. % tin and 0.5 wt. % chlorine. Finally, acontact material of lithium/tin/chloride/magnesium oxide was prepared byimpregnating 40 grams of magnesium oxide with 10.5 grams tin chloride(SnCl₄ ·H₂ O) dissolved in 50 milliliters of water, drying the same,then impregnating with 2.1 grams of lithium nitrate dissolved in 50milliters of water, again drying and calcining for 3 hours at 815° C. inair. The calculated content of this contact material was 8.2 wt. % tinand 0.5 wt. % lithium. Atomic absorption analysis showed the catalyst tocontain 20 wt. % tin, 1.1 wt. % lithium and 4.7 wt. % chlorine.

These contact materials were then utilized to produce ethylene fromethane by oxidative dehydrogenation. Fifteen milliliter portions of thecontact materials (screened to -16 to +40 mesh) were placed in a quartzreactor having a temperature controlled furnace. Gases were flowedthrough the contact material in a downflow fashion. Nitrogen was firstflowed through the contact material to heat the same to about 700° C.The nitrogen was stopped and a mixture of air and ethane was then flowedover the contact material at 400 GHSV ethane and 1200 GHSV air. Snapsamples were taken at appropriate times and analyzed by chromatographicanalysis. The results of these runs are shown in the following table.

                                      TABLE I                                     __________________________________________________________________________                               %     %     %                                      Contact   GHSV                                                                              Vol  Temp.                                                                             Time                                                                              Conversion                                                                          Selectivity                                                                         Yield                                  Material* Total                                                                             C.sub.2 H.sub.6 /O.sub.2                                                           °C.                                                                        min.                                                                              C.sub.2                                                                             C.sub.2 ═                                                                       C.sub.2 ═                          __________________________________________________________________________    MgO       1600                                                                              1.67/1                                                                             700 60  30.6  55.9  17.11                                  (Control)                                                                     MgO       1600                                                                              1.67/1                                                                             700 660 25.7  54.1  13.90                                  (Control)                                                                     0.5 Li/MgO                                                                              1600                                                                              1.67/1                                                                             700 60  55.6  92.1  51.21                                  0.5 Li/MgO                                                                              1600                                                                              1.67/1                                                                             700 960 32.5  92.6  30.10                                  2.5 Sn/MgO                                                                              1600                                                                              1.67/1                                                                             700 60  60.9  68.3  41.59                                  2.5 Sn/MgO                                                                              1600                                                                              1.67/1                                                                             700 120 60.0  68.0  40.80                                  6.3 Li/2.5 Sn/MgO                                                                       1600                                                                              1.67/1                                                                             700 60  47.3  85.6  40.49                                  8.2 Sn/0.5 Cl/MgO                                                                       1600                                                                              1.67/1                                                                             700 60  80.6  72.3  58.27                                  1.1 Li/20 Sn/                                                                 4.7 Cl/MgO                                                                              1600                                                                              1.67/1                                                                             700 60  61.6  94.6  58.27                                  1.1 Li/20 Sn/                                                                 4.7 Cl/MgO                                                                              1600                                                                              1.67/1                                                                             700 240 35.7  96.3  34.38                                  __________________________________________________________________________     *All contact materials are in weight percent of the indicated element         based on the total weight of MgO and the compound or compounds in which       the element or elements are contained.                                   

It is quite apparent from the foregoing table that the contact materialscontaining lithium, tin, lithium/tin, tin/chloride andlithium/tin/chloride were all vastly superior to magnesium oxide alone,both in the conversion of ethane and the selectivity to ethylene.Comparison of the contact materials containing chloride with those notcontaining chloride shows that chloride further enhanced the activity ofthe contact materials. Chloride analysis of the contact materialcontaining lithium/tin/chloride, following four hours of use, showed thechloride concentration had decreased to about 0.3 wt. %. A very distinctadvantage of the contact material of the present invention and theprocess is that the process can be carried out in a continuous mannerand, as such, can normally be operated at lower temperatures thanconventional, alternate ethane and air, has reduced energy requirements,since the exothermic and endothermic steps occur simultaneously, asopposed to separately as in a cyclic operation where the hydrocarbonsand oxygen-containing gas are sequentially passed through the contactmaterial, has reduced commercial construction costs, since there is noneed for rapid recycle and cycling, can use a fixed bed reactor and canextend the useful life of the contact material.

The present invention is further illustrated by the following examples,utilizing contact materials of the present invention, for the oxidativeconversion of methane to ethane and ethylene, particularly the latter,in the presence of a free oxygen containing gas.

The solid contact materials utilized in the examples were prepared bymixing the ingredients, for example, lithium carbonate and calciumhydroxide, in a blender with enough water to form a thick slurry. Thematerial was calcined overnight at 300° C. and, thereafter, for fourhours at 775° C. to produce a contact material containing the specifiedweight percent of the component present in a minor amount, for example 3wt. % lithium.

In the runs of the examples, the contact material was loaded in a quartzreactor having a thermocouple well centered in the contact material bed.The reactor was brought up to temperature under nitrogen or air and,thereafter, methane and air (or oxygen) flow was begun. The gas inletsystem included electronic flow measurement, a three-zone furnace forheating reactant gases and the contact material and a downstreamanalysis system. The reactor effluent was snap sampled at any desiredtime and analyzed for all paraffins and olefins between C₁ and C₄ andN₂, O₂, CO and CO₂ by gas chromatography. All contact materials arereferred to in terms of weight percent of the designated element basedon the total weight of the contact material.

The variables and results of this series of tests are set forth in TableII below. Conversion is percent of methane converted. Selectivity andyields are based on mole percent of methane feed converted to aparticular product. The CH₄ rate can be expressed as cc/min/cc ofcontact material. For example, when 70 cc/min of CH₄ was fed to areactor containing 20 cc of catalyst the flow rate would be 3.5 cc/minof CH₄ /cc of contact material. The volumetric ratio of CH₄ to oxygen isalso parenthetically given in terms of cc/min of CH₄ per cc/min of othergases (air or N₂) percent. The active metals of the contact materials,which are present in minor amounts, were in their oxide form and, aspreviously indicated, the percent of such active metal listed is theweight percent of elemental active metal based on the total weight ofthe active metal compound and the base metal compound.

                                      TABLE II                                    __________________________________________________________________________                     Vol. of                                                                           Sample                                                   Run                                                                              Contact Vol., cc                                                                            Con.                                                                              Time                                                                              Temp.                                                                             Conver-                                                                            Selectivity         Conversion To           No.                                                                              Material                                                                              CH.sub.4 /Air                                                                       Mat (min)                                                                             (°C.)                                                                      sion C.sub.2 ═                                                                    C.sub.2                                                                          C.sub.2 's                                                                       C.sub.3 ═                                                                    C.sub.3                                                                         CO.sub.2                                                                         CO C.sub.2 ═                                                                    C.sub.2 's                                                                       HC's              __________________________________________________________________________    1  MgO     70/80 20 cc                                                                             6   700 14.5 8.5                                                                              10.1                                                                             18.6                                                                             -- --                                                                              51.3                                                                             30.1                                                                             1.23                                                                             2.70                                                                             2.70                                   60  705 15.7 6.8                                                                              8.9                                                                              15.7                                                                             0.1                                                                              --                                                                              54.7                                                                             29.5                                                                             1.07                                                                             2.46                                                                             2.48              2  Na(3%)/MgO                                                                            70/80 20 cc                                                                             5   710 20.2 29.5                                                                             22.9                                                                             52.4                                                                             2.7                                                                              0.9                                                                             41.3                                                                             2.6                                                                              5.96                                                                             10.52                                                                            11.31                                  45  716 20.2 31.2                                                                             22.5                                                                             53.7                                                                             2.9                                                                              0.9                                                                             39.5                                                                             3.0                                                                              6.30                                                                             10.85                                                                            11.62                                  80  716 19.1 33.2                                                                             23.8                                                                             57.0                                                                             -- --                                                                              39.7                                                                             3.2                                                                              6.34                                                                             10.89                                                                            10.89             3  Li(3%)/CaO                                                                            70/80 20 cc                                                                             17  707 18.0 40.9                                                                             27.3                                                                             68.0                                                                             3.7                                                                              --                                                                              25.3                                                                             2.7                                                                              7.36                                                                             12.24                                                                            12.91                                  53  711 19.0 38.7                                                                             28.6                                                                             67.3                                                                             3.7                                                                              1.0                                                                             24.9                                                                             3.1                                                                              7.35                                                                             12.79                                                                            13.68                                  90  711 18.0 38.3                                                                             26.6                                                                             64.9                                                                             3.8                                                                              1.1                                                                             26.9                                                                             3.4                                                                              6.89                                                                             11.68                                                                            12.56                                  1050                                                                              710 17.3 36.0                                                                             25.8                                                                             61.8                                                                             3.2                                                                              --                                                                              29.9                                                                             5.1                                                                              6.23                                                                             10.69                                                                            11.25             4  Na(3%)/CaO                                                                            70/80 20 cc                                                                             70  731 18.9 36.1                                                                             29.2                                                                             65.3                                                                             3.4                                                                              2.0                                                                             27.3                                                                             1.9                                                                              6.82                                                                             12.34                                                                            13.36                                  120 709 15.7 35.3                                                                             35.0                                                                             70.3                                                                             2.9                                                                              2.2                                                                             24.6                                                                             -- 5.54                                                                             11.04                                                                            11.84                        50/100                                                                              20 cc                                                                             5   717 21.7 36.0                                                                             25.8                                                                             61.8                                                                             2.8                                                                              1.6                                                                             31.8                                                                             1.9                                                                              7.81                                                                             13.41                                                                            14.37                                  40  719 21.8 38.4                                                                             28.2                                                                             66.6                                                                             2.8                                                                              --                                                                              28.4                                                                             2.2                                                                              8.37                                                                             14.52                                                                            15.13             5  K(3%)/CaO                                                                             100/100                                                                             25 cc                                                                             6   710 10.7 19.5                                                                             36.0                                                                             55.5                                                                             1.1                                                                              1.7                                                                             36.0                                                                             2.6                                                                              2.09                                                                             5.94                                                                             6.24                                   51  704 8.5  19.9                                                                             44.8                                                                             64.7                                                                             -- --                                                                              35.3                                                                             -- 1.69                                                                             5.50                                                                             5.50                                   96  702 9.8  19.0                                                                             38.9                                                                             57.9                                                                             1.2                                                                              1.9                                                                             36.1                                                                             2.8                                                                              1.86                                                                             5.67                                                                             5.98                                   130 700 9.9  19.5                                                                             38.6                                                                             58.1                                                                             -- --                                                                              39.0                                                                             2.9                                                                              1.93                                                                             5.75                                                                             5.75              6  Li(3%)/CaO                                                                            70/80 20 cc                                                                             40  703 0.28 -- -- -- -- --                                                                              100                                                                              -- -- -- --                           (CH.sub.4 /N.sub.2)                                                                         703 0.28 -- -- -- -- --                                                                              100                                                                              -- -- -- --                                         702 0.06 -- -- -- -- --                                                                              99.99                                                                            -- -- -- --                7  Quartz  70/80 20 cc                                                                             40  740 0.00 -- -- -- -- --                                                                              -- -- -- -- --                __________________________________________________________________________

While specific materials, equipment, conditions and modes of operationhave been set forth herein, it is to be understood that these specificrecitals are by way of illustration and to set forth the best mode only,and are not to be considered limiting.

That which is claimed:
 1. A solid composition of matter consistingessentially of: (a) a component comprising lithium, and (b) a componentcomprising magnesium and (c) a component comprising (1) at least onematerial selected from the group consisting of tin and compoundscontaining tin and (2), optionally, at least one material selected formthe group consisting of chloride ions and compounds containing saidchloride ions.
 2. A composition in accordance with claim 1 wherein saidlithium is present in an amount between about 0.1 and about 50 wt. %,expressed in terms of the element, based on the total weight of saidcomposition.
 3. A composition in accordance with claim 1 wherein saidtin is present in an amount between about 0.5 and about 20 wt. %,expressed in terms of the element, based on the total weight of saidcomposition.
 4. A composition in accordance with claim 3 wherein saidlithium is present in an amount between about 0.1 and about 50 wt. %,expressed in terms of the element, based on the total weight of saidcomposition.